EP1902116B1 - Process for improving the quality as a fuel of hydrotreated hydrocarbon blends - Google Patents

Process for improving the quality as a fuel of hydrotreated hydrocarbon blends Download PDF

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Publication number
EP1902116B1
EP1902116B1 EP06762434A EP06762434A EP1902116B1 EP 1902116 B1 EP1902116 B1 EP 1902116B1 EP 06762434 A EP06762434 A EP 06762434A EP 06762434 A EP06762434 A EP 06762434A EP 1902116 B1 EP1902116 B1 EP 1902116B1
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hydrotreated
process according
ranging
alumina
blends
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English (en)
French (fr)
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EP1902116A1 (en
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Roberto Giardino
Vincenzo Calemma
Ugo Cornaro
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Eni SpA
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Eni SpA
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • B01J29/7469—MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7669—MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/643—Pore diameter less than 2 nm
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1051—Kerosene having a boiling range of about 180 - 230 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/307—Cetane number, cetane index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

Definitions

  • the present invention relates to a process for improving the quality as a fuel of hydrotreated hydrocarbon blends.
  • a partial dearomatization process of hydrotreated hydrocarbon blends with the limited formation of products have a lower molecular weight with respect to the charge.
  • the hydrotreated hydrocarbon blends can be hydrotreated oil cuts or hydrotreated cuts of a petrochemical origin. This process comprises the enrichment of blends resulting in alkyl-benzene compounds, at least partially deriving from the conversion of the naphtho-aromatic structures contained in said hydrotreated blends.
  • the process of the present invention produces an increase in the cetane index and a reduction in the density of the blends obtained, wherein said reduction in the density is equivalent to that obtained by means of total dearomatization, but it is effected with a much lower hydrogen consumption.
  • the process is carried out in the presence of a bifunctional catalytic system comprising one or more metals selected from Pt, Pd, Ir, Rh, Ru and Re, and a micro-mesoporous silico-alumina having a suitable composition as defined in claim 1.
  • the catalysts generally used in this process consist of a metallic phase deposited on a carrier having a medium-low acidity. It should be pointed out, however, that the hydrogenation of the aromatic structures causes high hydrogen consumptions.
  • the catalysts used in this case are of the bifunctional type, i.e. consisting of metals which have a dehydrogenating function supported on a generally more acid phase than that of the carriers used in the previous case.
  • MI2004A000798 describes the upgrading of distillates containing naphthene compounds by the transformation of these compounds into the corresponding paraffinic derivatives, which uses catalysts containing Pt, Pd, Ir, Rh, Ru and Re and an acid silico-aluminate selected from a suitable micro-mesoporous silico-alumina and an MTW zeolite.
  • US 2002/0050466 discloses a process for opening naphthenic rings and catalysts which can be used in that process.
  • the Applicants have now unexpectedly found a process which produces a substantial improvement in the properties of hydrotreated hydrocarbon cuts, in particular in terms of cetane index (number), density and distillation curve, which has proved to be equivalent to that obtained by the simple hydrogenation of aromatic structures.
  • the process, object of the invention causes a negligible formation of low molecular weight products and requires lower hydrogen consumptions with respect to the known processes.
  • a first object of the present invention therefore relates to a process for improving the properties as a fuel of hydrotreated hydrocarbon blends which comprises the treatment of said blends, in the presence of hydrogen, with a catalytic system comprising:
  • the hydrotreated hydrocarbon blends used in the process of the present invention can derive from oil cuts or cuts of a petrochemical origin which have been subjected to hydrotreatment.
  • the process of the present invention allows a substantial increase in the cetane index (number) to be obtained together with a decrease in the density and T95 of the hydrotreated hydrocarbon blends.
  • the blends thus obtained are, among other things, enriched in alkylbenzene compounds which at leat partially derive from the partially hydrogenated polycyclic aromatic compounds of the benzonaphthene type present in the hydrocarbon cuts which have undergone a hydrotreatment.
  • the catalysts used in the present invention are therefore unexpectedly capable of directing the process towards the formation of alkylbenzene structures by the hydrodecyclization of the naphthene ring of naphtho-benzene or dinaphtho-benzene structures, thus obtaining the best possible compromise between hydrogen consumption and improvement in the properties of the product, at the same time limiting both the complete hydrogenation reaction of the aromatic rings and the cracking reaction to form light products.
  • the formation of light products by means of the hydrocracking reaction should this take place, would, in this case, have a double disadvantage: a decrease in the yields in the product of interest and a greater hydrogen consumption.
  • a preferred aspect is for the molar ratio SiO 2 /Al 2 O 3 to range from 50 to 300. According to another preferred aspect, the silico-alumina has a porosity ranging from 0.4 to 0.5 ml/g.
  • MSA Completely amorphous micro-mesoporous silico-aluminas which can be used for the present invention, called MSA, and their preparation are described in US 5,049,536 , EP 659,478 , EP 812,804 .
  • MSA amorphous micro-mesoporous silico-aluminas
  • Their XRD spectrum from powders does not have a crystalline structure and does not show any peak.
  • the silico-aluminas which can be adopted for the process of the present invention can be prepared, according to EP 659,478 , starting from tetra-alkylammonium hydroxide, an aluminum compound hydrolyzable to Al 2 O 3 , and a silicon compound hydrolyzable to SiO 2 , wherein said tetra-alkylammonium hydroxide is a tetra(C 2 -C 5 ) alkylammonium hydroxide, said hydrolyzable aluminum compound is an aluminum tri(C 2 -C 4 )-alkoxide and said hydrolyzable silicon compound is a tetra(C 1 -C 5 ) alkylorthosilicate: these reagents are subjected to hydrolysis and gelification operating at a temperature equal to or higher than the boiling point, at atmospheric pressure, of any alcohol which is formed as byproduct of said hydrolysis reaction, without the elimination or substantial elimination of said alcohols from the reaction environment.
  • the gel thus produced is dried and calcined, preferably in an oxidizing atmosphere at a temperature ranging from 500 to 700°C, for a period of 6-10 hours.
  • the procedure comprises preparing an aqueous solution of tetra-alkylammonium hydroxide and aluminum trialkoxide and the tetra-alkylorthosilicate is added to this aqueous solution, operating at a temperature lower than the hydrolysis temperature, with a quantity of reagents which is such as to respect the molar ratios SiO 2/ Al 2 O 3 from 30/1 to 500/1, tetra-alkylammonium hydroxide/SiO 2 from 0.05/1 to 0.2/1 and H 2 O/SiO 2 from 5/1 to 40/1, and the hydrolysis and gelification are triggered by heating to a temperature higher than about 65°C to about 110°C, operating in an autoclave at the autogenous pressure of the system or at atmospheric pressure in a reactor equipped with a condenser.
  • the metallic component of the catalytic compositions used in the process of the present invention is selected from Pt, Pd, Ir, Ru, Rh, Re and their mixtures.
  • the metal is platinum, iridium or their mixtures.
  • the metal or mixture of metals is preferably in a quantity ranging from 0.1 to 5% by weight with respect to the total weight of the catalytic composition, and preferably ranges from 0.3 to 1.5%.
  • the weight percentage of the metal, or metals refers to the metal content expressed as metallic element; in the final catalyst, after calcination, said metal is in the form of an oxide.
  • the catalyst Before being used, the catalyst is activated by the known techniques, for example by means of a reduction treatment, and preferably by drying and subsequent reduction.
  • the drying is carried out in an inert atmosphere at temperatures ranging from 25 to 100°C, whereas the reduction is obtained by thermal treatment of the catalyst in a reducing atmosphere (H 2 ) at a temperature ranging from 300 to 450°C, and a pressure preferably ranging from 1 to 50 atm.
  • a reducing atmosphere H 2
  • the silico-alumina of the catalyst used in the process of the present invention can be in the form of an extruded product with traditional ligands, such as for example aluminum oxide, bohemite or pseudobohemite.
  • the extruded product can be prepared according to the methods well known to experts in the field.
  • the silico-alumina and the ligand can be premixed in weight ratios ranging from 30:70 to 90:10, preferably from 50:50 to 70:30.
  • the product obtained is consolidated into the desired final form, for example in the form of extruded pellets or tablets.
  • the metallic phase (a) of the catalyst is wet with an aqueous solution of a compound of the metal, operating, for example, at room temperature, and at a pH ranging from 1 to 4.
  • the aqueous solution preferably has a metal concentration expressed as g/l ranging from 0.2 to 2.0.
  • the resulting product is dried, preferably in air, at room temperature, and is calcined in an oxidizing atmosphere at a temperature ranging from 200 to 600°C.
  • the acid component (b) is suspended in an alcohol solution containing the metal. After impregnation, the solid is dried and calcined.
  • the acid component (b) is suspended in an aqueous solution of a complex or salt of the metal, operating at room temperature and at a pH ranging from 6 to 10.
  • the solid is separated, washed with water, dried and finally thermally treated in an inert or oxidizing atmosphere.
  • Temperatures useful for the purpose are those ranging from 200 to 600°C.
  • Metal compounds which can be used in the preparations described above are: H 2 PtCl 6 , Pt(NH 3 ) 4 (OH) 2 , Pt(NH 3 ) 4 Cl 2 , Pd(NH 3 ) 4 (OH) 2 , PdCl 2 , H 2 IrCl 6 , NH 4 ReO 4 , RuCl 3 , RhCl 3 .
  • the impregnation is carried out as follows: the acid component (b), also in extruded form, is wet with a solution of a compound of a first metal, the resulting product is dried, it is optionally calcined, and is impregnated with a solution of a compound of a second metal.
  • a calcination is then effected in an oxidizing atmosphere at a temperature ranging from 200 to 600°C.
  • a single aqueous solution containing two or more compounds of different metals can be used for contemporaneously introducing said metals.
  • hydrotreated hydrocarbon blends which can be subjected to the process of the present invention are blends having boiling points ranging from about 50°C to about 450°C, preferably from 150°C to 400°C, more preferably from 180°C to 380°C at atmospheric pressure.
  • the hydrocarbon cuts can be obtained by the hydrotreatment of oil cuts such as naphthas, diesel, kerosene, jet fuel, light cycle oil (LCO), HVGO or FCC heavy fraction, or by the hydrotreatment of cuts of a petrochemical origin, such as, for example, FOK (fuel oil cracking).
  • oil cuts such as naphthas, diesel, kerosene, jet fuel, light cycle oil (LCO), HVGO or FCC heavy fraction
  • LCO light cycle oil
  • FCC heavy fraction or by the hydrotreatment of cuts of a petrochemical origin, such as, for example, FOK (fuel oil cracking).
  • the hydrocarbon cuts subjected to hydrotreatment for providing the hydrotreated hydrocarbon blends used in the process of the present invention have a content of aromatic compounds preferably greater than 20%, and even more preferably greater than 40%, mainly consisting of mono-aromatic compounds, diaromatic compounds and, to a lesser degree, triaromatic compounds.
  • the hydrotreatment varies the nature and composition of the hydrocarbon cut subjected thereto and, among other things, enriches the cut in benzonaphthene compounds.
  • Hydrotreatment is a process which is well-known to experts in the field and is described, for example, in Catalysis-Science and Technology, Edited by R. Anderson and M. Boudart, Volume 11, Springer-Verlag, of 1996 . It can be effected in one or more fixed bed reactors, and the catalytic beds can contain the same or different catalysts.
  • Catalysts based on metallic compounds of Group VI, and/or Group VIII are usually used, on a carrier, preferably an amorphous carrier, such as, for example, alumina or silica-alumina.
  • Metals which can be well used are, for example, nickel, cobalt, molybdenum and tungsten. Examples of suitable catalysts and their preparation are described in Hydrocracking Science and Technology, J. Scherzer and A.J. Gruia, Marcel Dekker, 1996 .
  • the hydrotreatment catalysts are used in sulfidated form.
  • the sulfidation can be obtained, for example, by sending a suitable charge onto the catalyst, containing a sulfurated compound such as Dimethyldisulfide (DMDS), Dimethylsulfoxide (DMSO) or other compounds which, upon decomposing, lead to the formation of H 2 S.
  • DMDS Dimethyldisulfide
  • DMSO Dimethylsulfoxide
  • the hydrotreatment is preferably carried out at a temperature ranging from 200°C to 400°C.
  • the pressure normally range from 20 to 100 bars, in relation to the catalyst used, an expert in the field can easily identify the best conditions for the catalyst selected.
  • the charge undergoes saturation reactions of the aromatic rings with a reduction in the content of aromatic carbon and an enrichment in naphtho-aromatic compounds.
  • the process of the present invention which allows an increase in the cetane number, a decrease in the density and T95 of hydrotreated hydrocarbon blends, is preferably carried out at a temperature ranging form 240 to 380°C, at a pressure ranging from 10 to 100 atm, at a WHSV ranging from 0.5 to 5 hours -1 and with a ratio between hydrogen and charge (H 2/ HC) ranging from 400 to 2000 Nlt/kg. It is preferable to operate at a pressure greater than 20 atm and lower than or equal to 80 atm, whereas the temperature preferably ranges from 300 to 380°C.
  • tetra-ethylammonium hydroxide at 40% by weight, in aqueous solution are added to 24 grams of demineralized water. 4 grams of sodium aluminate at 56% by weight of Al 2 O 3 are then added.
  • the limpid solution thus obtained is poured, under stirring, into 350 grams of Ludox HS 40 colloidal silica. After brief stirring, a limpid homogenous gel is obtained which is poured into a 1 litre autoclave made of AISI 316, equipped with an anchor stirrer. The gel is left to crystallize under hydrothermal conditions at 160°C for 60 hours. At the end of this phase, the autoclave is cooled to room temperature.
  • the slurry obtained is homogeneous, with a milky appearance.
  • the slurry is centrifuged.
  • the discharged solid is washed by redispersion in water, centrifuged again, dried at 120°C and calcined at 550°C for 5 hours.
  • the solid obtained Upon X-ray diffraction analysis, the solid obtained proves to consist of pure ZSM-12.
  • the solid obtained is subsequently exchanged into ammonia form by treatment with a solution of ammonium acetate 3 M. Upon subsequent calcination at 550°C for 5 hours, the zeolite in acid form is obtained.
  • a volume of 200 ml of this solution was added to 30 g of the zeolite prepared as described above, so that all the solid was covered by the solution, to avoid heterogeneity in the platinum distribution.
  • the suspension thus obtained was maintained under stirring for about an hour at room temperature and subsequently degassed by suction under vacuum (about 18 mmHg) at room temperature.
  • the solvent was subsequently removed by heating to about 70°C under vacuum.
  • the dry product was finally calcined under a stream of air with the following temperature profile 25-350°C in two hours, 360°C for 3 hours.
  • a ZSM-12 zeolite is obtained, containing 1.0% by weight of platinum.
  • catalyst B ZSM-12/1% Ir (not according to the invention).
  • a volume of 400 ml of this solution was added to 30 g of the solid prepared as described in the previous step (a), so that all the solid is covered by the solution, in order to avoid heterogeneity in the iridium distribution.
  • the suspension thus obtained is maintained under stirring for about an hour at room temperature and subsequently degassed by suction under vacuum (about 18 mmHg) at room temperature.
  • the solvent is subsequently removed by heating to about 70°C under vacuum.
  • the dry product is finally calcined under a stream of air with the following temperature profile 25-350°C in two hours, 350°C for 2 hours, 350-400°C in 50 min., at 400°C for 3 hours.
  • a ZSM-12 zeolite is obtained, containing 1% of Iridium.
  • the product is left to rest for about 6-8 hours and is then dried by maintaining it in a stream of air at 100°C until the weight becomes constant. It is finally calcined in a muffle at 550°C for 8 hours in air.
  • the solid Upon X-ray analysis, the solid proves to be substantially amorphous, the XRD spectrum from powders does not have a crystalline structure and does not show any peak.
  • a volume of 400 ml of this solution was added to 30 g of the solid prepared as described in the previous step (a), so that all the solid was covered by the solution, to avoid heterogeneity in the platinum distribution.
  • the suspension thus obtained was maintained under stirring for about an hour at room temperature and subsequently degassed by suction under vacuum (about 18 mmHg) at room temperature.
  • the solvent was subsequently removed by heating to about 70°C under vacuum.
  • the dry product was finally calcined under a stream of air with the following temperature profile 25-350°C in two hours, 350°C for 2 hours, 350-400°C in 50 min., 400°C for 3 hours.
  • a silico-alumina of the MSA type is obtained, containing 1% by weight of platinum.
  • a volume of 400 ml of this solution was added to 30 g of the solid prepared as described in the previous step (a), so that all the solid is covered by the solution, in order to avoid heterogeneity in the iridium distribution.
  • the suspension thus obtained is maintained under stirring for about an hour at room temperature and subsequently degassed by suction under vacuum (about 18 mmHg) at room temperature.
  • the solvent is subsequently removed by heating to about 70°C in a stream of air.
  • the dry product is finally calcined under a stream of air with the following temperature profile 25-350°C in two hours, 350°C for 2 hours, 350-400°C in 50 min., at 400°C for 3 hours.
  • a silico-alumina of the MSA type is obtained, containing 1% of Ir.
  • Catalyst E Al 2 O 3 -B/l% Pt
  • An aluminum borate is prepared in accordance with EP 667,184 using the following procedure: 40 g of alumina in extruded form with a surface area of 200 m 2 /g are immersed in 80 ml of an aqueous solution containing 2.06 g of H 3 BO 3 and left at 70°C for 23 hours. The solid is separated from the water by filtration and is then washed on a filter, dried at 120°C for 16 hours and calcined at 550°C for 3 hours. Chemical analysis reveals a content of B 2 O 3 of 2.1% by weight.
  • alumina borate obtained in the previous step are impregnated with the incipient wettability technique. 25 cc of solution are required, corresponding to a wettability of 0.693 cc/gr.
  • the solution is prepared by weighing 4.0 g of an aqueous solution at 9.11% of Pt(NH 3 ) 4 (OH) 2 brought to a total volume of 25 cc with water. The solution is dried at 120°C for a night, and is then calcined at 360°C for 3 hours. An aluminum borate is obtained, containing 1% of Pt.
  • the catalytic tests were carried out on a continuous laboratory plant shown in Figure 1 .
  • the system consisted of a tubular fixed bed reactor (4) with a useful volume of the charge of 20 cm 3 corresponding to a height of the catalytic bed in the isotherm section of 10 cm.
  • the feeding of the charge, contained in the tank (1) and hydrogen to the reactor are effected by means of a dosage pump (2) and a mass flow meter, respectively.
  • the system is also equipped with two gas lines (air and nitrogen) which are used in the regeneration phase of the catalyst.
  • the reactor operates in an equicurrent down flow system.
  • the temperature of the reactor is regulated by means of an oven with two heating elements (3) whereas the temperature control of the catalytic bed is effected by means of a thermocouple (10) positioned inside the reactor.
  • the pressure of the reactor is regulated by means of a valve (8) situated downstream of the reactor.
  • the reaction products are collected in a separator (5) which operates at room temperature and atmospheric pressure.
  • the products leaving the separator (5) pass into a condenser (6) cooled to 5°C and are subsequently sent to a gas meter (C.L.) (7) and then to the blow-down (B.D.).
  • (9) is the breakage disk.
  • the distribution of the products and conversion level are determined by means of mass balance and gas chromatographic analysis of the reaction products.
  • Catalysts A, B, C, D and E of examples 1, 2, 3, 4 and 5 were tested in the process of the present invention, in the equipment described above, using hydrotreated LCO as substrate, whose characteristics are indicated in the following Table A.
  • Table A Density 15°C, g/cm 3 0.888 Distillation ASTM D86 IBP (Initial boiling point)°C 199 10%v, °C 220 30%v, °C 246 50%v, °C 260 70%v, °C 280 90%v, °C 312 FBP (final boiling point)°C 342 Cetane index (4V) 34.2
  • the percentage of alkylbenzenes in the hydrotreated charge is equal to 7.6% of the aromatic compounds present.
  • the pressure in the reactor is maintained at between 2.0 and 6.0 MPa (20 and 60 atm).
  • the data in the first line of Table B refer to the characteristics of the hydrotreated blend before being fed to the process of the present invention.
  • the data indicated in the last column of Table C represent the relative hydrogen consumption taking 100% as the hydrogen consumption obtained using the comparative catalyst E at 280°C.
  • the catalytic tests were carried out on a pilot plant in continuous.
  • the system consisted of a 1825 mm fixed bed tubular reactor having an internal diameter of 40 mm with a useful charge volume of 800 cm 3 .
  • the feeding of the charge, contained in the tank and of the hydrogen to the reactor are effected by means of a dosage pump and mass flow meter, respectively.
  • the reactor runs in an equicurrent down flow system.
  • the temperature of the reactor is regulated by means of six electrically heated outer blocks whereas the temperature control of the catalytic bed is effected by means of 18 thermocouples positioned inside the reactor in a sheath having an outer diameter of 10 mm.
  • the pressure of the reactor is regulated by means of a valve situated downstream of the reactor.
  • the gases are separated in a separator which operates under pressure and the reaction products are collected in a separator which operates at room temperature and atmospheric pressure.
  • the products leaving the high and low pressure separator pass into a cooled condenser and are subsequently sent to a gas meter and then to the blow-down.
  • the distribution of the products and the conversion level are determined by means of mass balance and gas chromatographic analysis of the reaction products.
  • the percentage of alkylbenzenes in the product is equal to 45.8% of the residual aromatic compounds.
  • Table E Density 15°C, g/cm 3 0.849 Distillation ASTM D86 IBP, °C 186 10%v, °C 214 30%v, °C 229 50%v, °C 244 70%v, °C 264 90%v, °C 303 FBP, °C 347 Cetane index (4V) 43.0 Aromatic compounds (HPLC) Mono-aromatic compounds, w% 0.8 Diaromatic compounds, w% 0.0 Triaromatic compounds, w% 0.0 Sulfur, ppm ⁇ 1 Nitrogen, ppm ⁇ 1 Hydrogen, % 14.35
  • the products obtained according to Example 7 have a higher content of aromatic compounds and a much lower hydrogen content.

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  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Hydrogen, Water And Hydrids (AREA)
EP06762434A 2005-07-08 2006-07-03 Process for improving the quality as a fuel of hydrotreated hydrocarbon blends Not-in-force EP1902116B1 (en)

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IT001295A ITMI20051295A1 (it) 2005-07-08 2005-07-08 Processo per migliorare le qualita' come carburante di miscele idrocarburiche idrotrattate
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2548572C2 (ru) * 2013-07-16 2015-04-20 Общество с ограниченной ответственностью "РИОС-Инжиниринг" Катализатор, способ его приготовления и способ одностадийного получения компонентов реактивных и дизельных топлив с улучшенными низкотемпературными свойствами и масложирового сырья

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20071610A1 (it) * 2007-08-03 2009-02-04 Eni Spa Processo integrato di cracking catalitico fluido per ottenere miscele idrocarburiche con elevate qualita' come carburante
US20090115060A1 (en) * 2007-11-01 2009-05-07 Infineon Technologies Ag Integrated circuit device and method
ITMI20080299A1 (it) * 2008-02-26 2009-08-27 Eni Spa Processo per migliorare le qualita' come carburante di miscele idrocarburiche idrotrattate
KR101503069B1 (ko) * 2008-10-17 2015-03-17 에스케이이노베이션 주식회사 유동층 접촉 분해 공정의 경질 사이클 오일로부터 고부가 방향족 및 올레핀을 제조하는 방법
TWI400619B (zh) * 2008-11-26 2013-07-01 Univ Nat Cheng Kung 偵測產品品質超規與評估產品實際量測值的方法
IT1392806B1 (it) 2009-02-02 2012-03-23 Eni Spa Processo integrato di cracking catalitico a letto fluido per ottenere miscele idrocarburiche con elevate qualita' come carburante
US20120000817A1 (en) * 2010-07-01 2012-01-05 Exxonmobil Research And Engineering Company Production of Low Color Middle Distillate Fuels
IT1401697B1 (it) 2010-09-10 2013-08-02 Eni Spa Processo e catalizzatori per migliorare le qualita' come carburante di miscele idrocarburiche
IT1403895B1 (it) 2010-12-29 2013-11-08 Eni Spa Processo e sistema catalitico per migliorare le qualita' come carburante di miscele idrocarburiche
EP2589434A1 (en) 2011-11-04 2013-05-08 ENI S.p.A. Process and catalysts for enhancing the fuel quality of hydrocarbon blends
DE102011118482A1 (de) * 2011-11-12 2013-05-16 Volkswagen Aktiengesellschaft Verfahren zur Cetanzahlanhebung von Naphtha
ITMI20112411A1 (it) 2011-12-28 2013-06-29 Eni Spa Metodo per individuare catalizzatori adatti a migliorare le qualità come carburante di miscele idrocarburiche e processo di upgrading che li utilizza
CN102658197A (zh) * 2012-05-16 2012-09-12 浙江师范大学 用于正构烷烃临氢异构化反应的催化剂及其制备方法和应用
JP2015528847A (ja) * 2012-07-31 2015-10-01 セタマックス ベンチャーズ リミテッド 炭化水素燃料の酸化及び水素化併用処理の方法及びシステム
EP2899252B1 (en) * 2012-09-21 2018-03-28 China Petroleum & Chemical Corporation Hydrocarbon oil hydrotreating method and apparatus
US9139783B2 (en) * 2012-11-06 2015-09-22 E I Du Pont Nemours And Company Hydroprocessing light cycle oil in liquid-full reactors
CN104588075B (zh) * 2013-10-30 2017-02-08 中国石油化工股份有限公司 一种烷基化催化剂的制备方法
EP3176243A1 (en) 2015-12-03 2017-06-07 SABIC Global Technologies B.V. Process for preparing a hydrocracking catalyst
WO2018025183A1 (en) 2016-08-02 2018-02-08 Sabic Global Technologies B.V. Process for preparing hydrocracking catalyst
WO2018160078A1 (es) * 2017-03-02 2018-09-07 Coquis Sanchez Concha Rodrigo Sistema mecánico de fluidos para la optimización del funcionamiento de aleaciones catalíticas para la mejora de propiedades y la eliminación de contaminantes microbiológicos en combustibles hidrocarburos
KR102504661B1 (ko) * 2017-08-18 2023-02-27 차이나 페트로리움 앤드 케미컬 코포레이션 중질 방향족 화합물로 경질 방향족 화합물을 제조하기 위한 촉매 및 이의 제조 방법과 용도

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3832449A (en) 1971-03-18 1974-08-27 Mobil Oil Corp Crystalline zeolite zsm{14 12
US4828675A (en) * 1987-12-04 1989-05-09 Exxon Research And Engineering Company Process for the production of ultra high octane gasoline, and other fuels from aromatic distillates
IT1219692B (it) 1988-05-06 1990-05-24 Eniricerche Spa Gel di silice e allumina cataliticamente attivo e procedimento per la sua preparazione
IT1256084B (it) * 1992-07-31 1995-11-27 Eniricerche Spa Catalizzatore per la idroisomerizzazione di normal-paraffine a catena lunga e procedimento per la sua preparazione
IT1265320B1 (it) 1993-12-22 1996-10-31 Eniricerche Spa Procedimento per la preparazione di silico-allumine amorfe cataliticamente attive
IT1276316B1 (it) 1994-02-11 1997-10-28 Snam Progetti Processo per l'isomerizzazione di scheletro di olefine lineari
US5831139A (en) * 1995-06-07 1998-11-03 Uop Llc Production of aliphatic gasoline
US5763731A (en) 1995-09-05 1998-06-09 Exxon Research And Engineering Company Process for selectively opening naphthenic rings
IT1284007B1 (it) 1996-06-13 1998-05-08 Eniricerche Spa Procedimento per la preparazione di un materiale micro-meso poroso ad alta area superficiale con distribuzione controllata della
US6103106A (en) 1997-08-22 2000-08-15 Exxon Research And Engineering Company Desulfurization and ring opening of petroleum streams
IT1312337B1 (it) * 1999-05-07 2002-04-15 Agip Petroli Composizione catalitica per l'upgrading di idrocarburi aventi punti di ebollizione nell'intervallo della nafta
US6589416B2 (en) 2000-07-21 2003-07-08 Exxonmobil Research And Engineering Company Method and catalyst for opening naphthenic rings of naphthenic ring-containing compounds
FR2826972B1 (fr) * 2001-07-06 2007-03-23 Inst Francais Du Petrole Procede de production de distillats moyens par hydroisomerisation et hydrocraquage d'une fraction lourde issue d'un effluent produit par le procede fischer-tropsch
KR20050085488A (ko) * 2002-12-09 2005-08-29 쉘 인터내셔날 리써취 마트샤피지 비.브이. 윤활제 제조 방법
ITMI20040798A1 (it) * 2004-04-23 2004-07-23 Eni Spa Processo e catalizzatori per l'apertura di anelli naftenici
US20050269245A1 (en) * 2004-06-03 2005-12-08 Huve Laurent G Process for desulphurising and dewaxing a hydrocarbon feedstock boiling in the gasoil boiling range

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2548572C2 (ru) * 2013-07-16 2015-04-20 Общество с ограниченной ответственностью "РИОС-Инжиниринг" Катализатор, способ его приготовления и способ одностадийного получения компонентов реактивных и дизельных топлив с улучшенными низкотемпературными свойствами и масложирового сырья
RU2548572C9 (ru) * 2013-07-16 2015-12-10 Общество с ограниченной ответственностью "РИОС-Инжиниринг" Катализатор, способ его приготовления и способ одностадийного получения компонентов реактивных и дизельных топлив с улучшенными низкотемпературными свойствами из масложирового сырья

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US20070187295A1 (en) 2007-08-16
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PT1902116E (pt) 2010-08-11
EA200702690A1 (ru) 2008-06-30
CA2614367A1 (en) 2007-01-18
CN101238201A (zh) 2008-08-06
ITMI20051295A1 (it) 2007-01-09
MX2008000348A (es) 2008-03-07
EA013273B1 (ru) 2010-04-30
WO2007006473A1 (en) 2007-01-18
US8236171B2 (en) 2012-08-07
CN101238201B (zh) 2013-01-09
BRPI0612664A2 (pt) 2012-10-02
EP1902116A1 (en) 2008-03-26
DE602006014151D1 (de) 2010-06-17
JP2009500478A (ja) 2009-01-08

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